Vulcanizable halogenated elastomer compositions

ABSTRACT

The invention provides articles obtained from curing a composition consisting of a polymercapto crosslinking agent, a vulcanization accelerator, an inorganic base, a nitrogen containing chelating agent, wherein the nitrogen containing chelating agent is selected from the group consisting of 1,10-phenanthroline and 2,2-bipyridyl, and polyethylenimine; and a halogenated elastomer; wherein said nitrogen containing chelating agent is soluble in said halogenated elastomer.

This application is a continuation application of U.S. patentapplication Ser. No. 11/719,222, filed on May 14, 2007, entitled,“VULCANIZABLE HALOGENATED ELASTOMER COMPOSITIONS,” which is a 371 U.S.national phase application of International Patent Application SerialNo. PCT/US05/46473, filed on Dec. 21, 2005, which is an application thatclaims the benefit of U.S. Provisional Application No. 60/638,093, filedon Dec. 21, 2004, the teachings of which are incorporated herein, intheir entirety, by reference, as if fully reproduced hereinbelow.

The present invention relates to an improved cure system for halogenatedelastomer compositions, comprising polymercapto crosslinking agents,vulcanization accelerators, an inorganic base, and a nitrogen containingchelating agent.

Halogenated elastomers may be cured by numerous means, including the useof peroxide/coagent systems, thiadiazole-based systems, or irradiationcrosslinking techniques. Peroxide cures are typically preferred fortheir scorch safety, shelf-life or bin stability, low permanent set, andhigh temperature performance. However peroxide cure systems are oftenunacceptable for use in molded goods, because of mold sticking andfouling due to volatiles, or in applications that require a lowtemperature cure, due to equipment or processing limitations.Thiadiazole-based cure systems provide certain advantages, such as theability to cure over a wider range of temperature and pressureconditions than peroxide cures, while generating fewer volatileby-products; good mold release characteristics, and the ability to useless expensive compounding ingredients, such as aromatic oils.

In U.S. Pat. No. 4,128,510, Richwine taught that halogen containingpolymers could be crosslinked by using 2,5-dimercapto-1,3,4-thiadiazole,or its derivatives, and a basic material. The basic materials includedmetal oxides, metal hydroxides, and metal carboxylates. The '510 patentalso taught that the addition of an accelerator containing aliphatic oraromatic amine structures or quaternary nitrogen groups may bedesirable. The condensation product of butyraldehyde and aniline wasclaimed as being a particularly useful accelerator. In a second patent,U.S. Pat. No. 4,288,576, Richwine expanded the use of2,5-dimercapto-1,3,4-thiadiazole and derivatives for curing saturatedhalogen containing elastomers, such as chlorinated polyethylene, byspecifically including certain vulcanization accelerators. Named classesof accelerators in the '576 patent were: 1) amines having a boilingpoint above 110° C., and having pK values below about 4.5; 2) salts ofamines, with pK values below 4.5 and acids having pK values above 2.0;3) quaternary ammonium hydroxides and their salts with acids, having apK above 2.0; 4) diphenyl- and ditolyl-guanidines; and 5) thecondensation product of aniline and mono-aldehydes containing one toseven carbon atoms. The '576 patent additionally required the presenceof at least an equal amount of an inorganic base.

Subsequent to the Richwine patents, several patents were issued claimingimproved 2,5-dimercapto-1,3,4-thiadiazole systems. Berta andKyllingstad, in U.S. Pat. No. 4,482,681, claimed that addition of asalt, with a contained water of hydration, could enhance the cure of2,5-dimercapto-1,3,4-thiadiazole systems, if such a salt released waterat temperatures above the compounding temperature, but below typicalcure temperatures. Magnesium sulfate heptahydrate, sodium sulfiteheptahydrate, and potassium aluminum sulfate dodecahydrate werespecifically claimed examples of such salts. Sauerbier et al., in U.S.Pat. No. 4,551,505 claimed that amidoamines, such as tetraethylenepentamine distearate, were more useful as accelerators, than eitheramines or aniline-butyaldehyde condensation products, because ofimproved vulcanizate properties and better mold release.

Honsberg, in U.S. Pat. No. 4,745,147, claimed that the addition ofpolyhydroxy alcohols to the cure system of metal oxide, amine, and2,5-dimercapto-1,3,4-thiadiazole, gave vulcanizates with improved heataging characteristics, by lowering the amount of basic metal oxiderequired. Salerno introduced a specific 2,5-dimercapto-1,3,4-thiadiazolederivative and aliphatic amine combination that he claimed was superiorto the 2,5-dimercapto-1,3,4-thiadiazole,monobenzoate-butyraldehyde-aniline condensation product system, becauseof improved bin stability of the mixed compound, and resistance to thebatch-to-batch cure variations inherent in that system (Salerno, M. “NewThiadiazole Cure System Offers Benefits to Chlorinated Polymers”,Elastomerics, April 1992). Class, in U.S. Pat. No. 5,665,830, claimedthat variability in the premature curing, or scorch, of the2,5-dimercapto-1,3,4-thiadiazole, amine, metal oxide system was due tothe influence of water, and that the variation could be eliminated byaddition of polyethylene glycol. In a subsequent patent, U.S. Pat. No.5,686,537, Class claimed the use of glycerin to similarly eliminate theinfluence of water on these cure systems.

Vulcanizable compositions of halogenated elastomers using polymercaptocompounds, other than 2,5-dimercapto-1,3,4-thiadiazole, have beendisclosed and studied. Mori and Nakamura published studies on the use of1,3,5-triazine-2,4,6-trithiol (Journal of Applied Polymer Science, Vol.30, p. 1049, 1985). They found that the use of onium compounds, such asquaternary ammonium or phosphonium salts, or polyethylene glycols, wereneeded to increase vulcanization rates, when1,3,5-triazine-2,4,6-trithiol is used to crosslink chlorinatedpolyethylenes. They suggested that the acceleration due to the use ofpolyethylene glycols was due to a mechanism similar to that of crownether accelerators on nucleophilic substitution.

Additional polymercapto based vulcanization systems for halogenatedelastomers, particularly co-curing rubber blends of halobutyl andepihalohydrin rubbers, were taught by Berta in U.S. Pat. No. 4,591,617.The '617 patent taught that treating trithiocyanuric acid,dithiohydantoins, dimercaptotriazoles, dithioltriazene, and variousderivatives of these compounds with inorganic base and accelerator wouldbe useful for curing chloroelastomers. Similar vulcanization systems forhalogenated elastomers based on dimercaptopyrazine ordimercaptoquinoxaline were proposed by Matoba in U.S. Pat. No.4,357,446.

Despite the excellent vulcanizate properties obtainable with thepolymercapto/metal (hydr)oxide/-accelerator-based vulcanization systemsfor halogenated elastomers, two key problems remain that limit theirusefulness. The first is premature vulcanization of the compound duringstorage, prior to forming the vulcanized article, and the second isinconsistency of the vulcanization rate. It is desired that theelastomer compound, after preparation, be stable under typicalenvironmental conditions of storage, such that minimal vulcanizationoccurs prior to formation of the finished article. A consistentvulcanization rate is desired so that processes that form the finishedvulcanized article, such as injection molding, extrusion, or compressionmolding, can be run consistently and without the generation of scrapmaterials.

The vulcanization rates of halogenated elastomer compositions thatcontain polymercapto compounds, such as 2,5-dimercapto-1,3,4-thiadiazoleand its derivatives, metal (hydr)oxides and their salts with weak acids,and vulcanization accelerators, such as quaternary ammonium compounds oramines, are extremely sensitive to the presence of certain commonimpurities, such as acidic fillers, chlorinated paraffins, isocyanates,epoxy, lead, and particularly zinc compounds, such as zinc oxide, atlevels as low as 50 ppm. Although efforts can be made to eliminate theseingredients from the desired composition, these impurities can remain ina piece of equipment from previous use, and inadvertently contaminatethe composition.

Zinc oxide is a common ingredient in the sulfur-based vulcanization of anumber of elastomers, and cross contamination of compounds is common inthe rubber industry. We have found that it is possible to eliminate orsignificantly reduce the effect of zinc oxide contamination on thevulcanization rates of polymercapto based vulcanization systems forhalogenated elastomers, by incorporation of nitrogen containingchelating compounds, such as 1,10-phenanthroline. While it is known thatsuch chelating agents bind transition metal compounds, it is surprisingthat they are effective at eliminating vulcanization rateinconsistencies due to ZnO contamination, without inducing negativechanges to the vulcanization reaction and the subsequent physicalproperties of the halogenated elastomer vulcanizate.

The invention provides for compositions comprising: a) a polymercaptocrosslinking agent, b) a vulcanization accelerator, c) an inorganicbase, and d) a nitrogen containing chelating agent that is soluble in ahalogenated elastomer. These compositions and further embodiments ofthese compositions are described herein. These compositions are used tocure halogenated elastomers as discussed herein. The invention alsoprovides for methods of curing a halogenated elastomer using theinventive compositions.

The invention provides for cured compositions formed an inventivecomposition as described herein. The invention also provides for anarticle comprising at least one component formed from an inventivecomposition as described herein. The invention further provides for anarticle comprising at least one component formed from a curedcomposition, which is formed form an inventive composition as describedherein.

In one embodiment, the composition contains a nitrogen containingchelating agent is an aromatic heterocyclic base containing a nitrogenbidentate ligand. In another embodiment, the nitrogen containingchelating agent is 1,10-phenanthroline. In yet another embodiment, thenitrogen containing chelating agent is 2,2-bipyridyl.

In another embodiment, the composition contains a nitrogen containingchelating agent, which is a tridentate nitrogen containing compound,selected from the group consisting of terpyridine, diethylenetriamine,and derivatives thereof. In yet another embodiment, the nitrogencontaining chelating agent is a tetradentate nitrogen containingcompound, selected from the group consisting of triethylenetetramine,porphyrin, phthalocyanine, and derivatives thereof. In yet a furtherembodiment, nitrogen containing chelating agent is a polyamine, selectedfrom the group consisting of an aziridine homopolymer,aziridine/1,2-diaminoethane copolymers, and the polymeric condensationproduct of ammonia and 1,2-dichloroethane.

In another embodiment, the composition contains a polymercapto curingagent, which is 2,5-dimercapto-1,3,4-thiadiazole or a derivativethereof. In yet another embodiment, the polymercapto curing agent is2-mercapto-1,3,4-thiadiazole-5-thiobenzoate.

-   -   In another embodiment, the composition contains a vulcanization        accelerator, which is selected from the group consisting of        quaternary ammonium or phosphonium salts, tertiary amines, and        dihydropyridine derivatives.        -   In another embodiment, the composition further contains a            halogenated elastomer. In a further embodiment, the            halogenated elastomer is selected from the group consisting            of polychloroprene, polyepichlorohydrin,            epichlorohydrin/ethylene oxide copolymers, a            chlorosulfonated polyethylene, a chlorinated polyethylene,            chlorinated ethylene alpha-olefin copolymers, copolymers of            vinylidene fluoride and hexafluoropropylene, and chlorinated            or brominated butyl rubbers. In yet another embodiment, the            halogenated elastomer is a chlorinated polyethylene.

The inventive compositions may contain combinations of two or moreembodiments as described herein. Methods of making the inventivecompositions, and articles prepared from such compositions, may alsocontain combinations of two or more embodiments as described herein.

Any polymer or copolymer containing halogen atoms that can be compoundedto form an elastomeric product upon crosslinking can be considered ahalogenated elastomer for the purposes of this invention. Examples ofhalogenated elastomers include, but are not limited to polychloroprene,polyepichlorohydrin, epichlorohydrin/ethylene oxide copolymers,chlorosulfonated polyethylene, chlorinated polyethylene, chlorinatedethylene alpha-olefin copolymers, copolymers of vinylidene fluoride andhexafluoropropylene, and chlorinated or brominated butyl rubbers.

Examples of chlorinated ethylene copolymers include those prepared fromcopolymers comprising ethylene and at least one ethylenicallyunsaturated monomer, selected from the group consisting of C₃-C₁₀ alphamonoolefins. Chlorinated graft copolymers are included as well. Specificexamples of suitable chlorinated ethylene copolymers, which may beemployed in the compositions of this invention, include copolymers ofethylene with propylene, 1-butene, 3-methyl-1-pentene, 1-pentene,1-hexene, 1-heptene or octene. The copolymers may be dipolymers,terpolymers, or higher order copolymers. Chlorinated polyethylene is apreferred chlorinated olefin elastomer. Some particular examples ofchlorinated elastomers are described further below. Chlorinated ethyleneester copolymers, such as ethylene methyl acrylate and ethylene methylmethacrylate, may also be suitable for used in the invention, if theester groups of such copolymers remain inert under the conditions ofcure.

Polymercapto crosslinking agents include2,5-dimercapto-1,3,4-thiadiazole, and its derivatives, as described inU.S. Pat. Nos. 4,128,510; 1,3,5-triazine-2,4,6-trithiol and itsderivatives; dimercaptotriazoles, as described in U.S. Pat. No.4,234,705; 2-4-dithiohydantoins, as described in U.S. Pat. No.4,342,851; and 2,3-dimercapto-pyrazine or -quinoxalines, as described inU.S. Pat. No. 4,357,446. Preferably, the crosslinking agent is2-mercapto-1,3,4-thiadiazole-5-thiobenzoate. The polymercapto compoundis typically incorporated at levels from 0.5 to 5 parts per hundredparts (phr) of the halogenated elastomer. All individual values andsubranges from 0.5 to 5 phr are included herein and disclosed herein.Each of these patents is incorporated herein, in its entirety, byreference.

Vulcanization accelerators useful in the composition include quaternaryammonium or phosphonium salts, tertiary amines, and dihydropyridinederivatives. Typical vulcanization accelerators includetetrabutylammonium bromide, tetrahexylammonium bromide,tetrabutylphosphonium chloride, orN-phenyl-3,5-diethyl-2-propyl-1,4-dihydropyridine. Vulcanizationaccelerators are incorporated at levels of 0.2-1 phr of the halogenatedelastomer. All individual values and subranges from 0.2 to 1 phr areincluded herein and disclosed herein.

Inorganic bases such as a metal oxide, hydroxide, or their salts withweak acids act as an acid acceptor to capture the hydrohalogen acid thatis formed as a byproduct of the curing reaction. Typical metals includethose of Group II of the periodic table, such as Mg, Ca, or Ba. Examplesof these compounds include, but are not limited to, magnesium oxide,magnesium hydroxide, calcium oxide, calcium hydroxide, barium hydroxide,magnesium carbonate, calcium carbonate and barium carbonate. Preferredbasic metal oxides and hydroxides are magnesium oxide and magnesiumhydroxide. The basic metal oxides are incorporated at levels of 2-10 phrof the halogenated elastomer. All individual values and subranges from 2to 10 phr are included herein and disclosed herein.

Nitrogen containing chelating compounds include bidentate nitrogencompounds, tridentate nitrogen compounds, tetradendate nitrogencompounds and polydentate nitrogen compounds. Each chelating compoundcontains two or more nitrogen atoms that are oriented in a configurationcapable of forming a coordination complex in association with a chargedor polarizable metal atom or other charged or polarizable moiety. Suchcompounds do not contain only two nitrogen atoms at para positions,relative to one another, on one or more aromatic rings.

Bidentate nitrogen compounds include, but are not limited to,ethylenediamine, 2,2′-bipyridine, 1,10-phenanthroline, and derivativesthereof. Such derivatives, as the term is used herein, are compoundsbased on the structure of the respective parent compound.

Tridentate nitrogen containing compounds, include, but are not limitedto, a terpyridine, diethylenetriamine, and derivatives thereof.Representative structures are shown below.

Tetradentate nitrogen containing compounds, include, but are not limitedto, triethylenetetramine, porphyrin, phthalocyanine, and derivativesthereof.

Polydentate nitrogen containing compounds, include, but are not limitedto, aziridine homopolymers (or polyethyleneimines),aziridine/1,2-diaminoethane copolymers, polymeric condensation productof ammonia and 1,2-dichloroethane, or derivatives thereof.Representative polyethyleneimines (PEIs) are polymeric amines with thegeneral backbone unit, —(CH₂—CH₂—NH)_(n)—, where “n” is from 10 to 10⁵.Polyethyleneimines may also include branched and/or sphericalpolyamines. In general, these structures usually have a well definedratio of primary, secondary and tertiary amine functions, and arecommercially available from BASF and Bayer. An example of a portion of arepresentative polyethyleneimine is shown below.

In one embodiment, nitrogen containing chelating compounds, suitable forused in the present invention, preferably do not contain anyheteroatoms, other than nitrogen and oxygen, and more preferably containonly hydrogen, carbon and nitrogen.

In another embodiment, the nitrogen containing chelating compoundcontains an N—C—C—N bonding sequence in the structure of the compound.In a further embodiment, the N—C—C—N bonding sequence is selected fromthe structures shown below:

The nitrogen containing chelating compound must be soluble or finelydispersible in the polymer phase of the compound in order to be aneffective component of the invention. Furthermore, it is preferable thatthe nitrogen containing chelating agent have a boiling point thatexceeds the temperature at which the elastomer compound is cured, sothat occupational exposure to the chelating agent and bubble formationin the finished elastomer product are minimized.

Some nitrogen containing chelating compounds, such asethylenediamine-tetraacetic acid (EDTA) and it salts, are not soluble ordispersible in many elastomer compounds, and therefore are noteffective. The magnitude of the effect at eliminating the cure rateinconsistency varies with the structure of the nitrogen containingchelating compound. Preferable nitrogen containing chelating agents are1,10-phenanthroline and its derivatives. Nitrogen containing chelatingagents are incorporated at levels from 0.2-2 phr of the halogenatedelastomer. Preferably, the level of the nitrogen containing chelatingagent is from 0.5-1.5 phr of the halogenated elastomer. All individualvalues and subranges from 0.2-2 phr are included herein and disclosedherein.

-   -   Compositions of the present invention may include other        ingredients commonly used in rubber vulcanization, such as        fillers, extenders, plasticizers, stabilizers, and pigments. The        properties of the final vulcanizate can be adjusted by addition        of these materials to suit the application. Examples of common        fillers are calcium carbonate, carbon black and clay. Extenders        and plasticizers are usually aromatic or napthenic oils or        esters. A typical pigment is titanium dioxide.

The ingredients of the elastomer composition are typically mixed anduniformly blended with the halogenated elastomeric polymer by use of ahigh intensity, internal mixer, such as a Banbury® mixer (FarrelCorporation). They may also be incorporated by milling on a two rollmill, or by any other mechanical mixing device from which a uniformblend of the ingredients can be derived. It is preferable to mix theingredients of the elastomeric composition such that the temperature ofthe composition does not exceed about 110° C., and the time of themixing is maintained, as short as is necessary, to achieve a uniformcomposition.

The mixing process may be improved by adding some of the ingredients ina binder. For example, reaction accelerators can be bound in a polymersuch as ethylene-propylene-diene rubber at concentrations of 25-75percent of the accelerator, thus making addition of small amounts ofingredient easier to handle. Whether the ingredients are added neat, oras binders, does not materially affect the results of this invention.

The conditions under which the elastomeric compound is crosslinked intothe elastomeric product, range from temperatures from 130° C. to 200°C., and from atmospheric to high pressures, such as those encountered incompression or injection molding. The time for the crosslinking reactionto take place varies with the temperature and the concentrations ofpolymercapto compound, accelerator, and metal oxide in the composition.Lower temperatures and lower concentrations require longer times for thefinished part to be crosslinked. Typical crosslinking times may be fromone minute to several hours.

Suitable chlorinated polyethylene elastomers may be selected from thegroup consisting of a) chlorinated polyethylene homopolymers preparedfrom polyethylenes having an 110 value of from 0.01-120 dg/min, and morepreferably from 0.05 to 100 dg/min, and b) chlorinated ethylenecopolymers prepared from ethylene copolymers having an 110 value of from0.01-120 dg/min that comprise copolymerized units of i) ethylene and ii)up to 25 weight percent (based on the total weight of monomers) of acopolymerizable monomer.

-   -   Some particular examples of halogenated elastomers include        chlorinated elastomers, as described in U.S. Pat. No. 6,720,383,        incorporated herein, in its entirety, by reference. Such        elastomers include a chlorinated olefin elastomer having a        chlorine content of from 15-48 percent by weight; said        chlorinated olefin elastomer is prepared from an olefin polymer        selected from the group consisting of: i) polyethylene        homopolymers having 110 values of from 0.05-0.8 dg/minute,        and ii) copolymers of ethylene and up to 25 weight percent of a        copolymerizable monomer, said copolymers having 110 values of        from 0.05-0.8 dg/minute.

In one embodiment, the chlorinated olefin elastomers useful in thepractice of the invention contain 15-48 weight percent chlorine,preferably 25 to 38 weight percent chlorine, based on the total weightof the elastomer. In another embodiment, the molecular weights of thenon-chlorinated polyolefin base resins range from approximately400,000-1,000,000 g/mole.

In another embodiment, the chlorinated olefin elastomers suitable foruse in the compositions of the invention may be prepared from polyolefinresins that are branched or unbranched. The polyolefin base resins maybe prepared by free radical processes, Ziegler-Natta catalysis, orcatalysis with metallocene catalyst systems, for example those disclosedin U.S. Pat. Nos. 5,272,236 and 5, 278,272, each incorporated herein, inits entirety, by reference.

Chlorine can be introduced to the polyethylene in a variety of ways:solution chlorination, aqueous slurry chlorination (Dow process forTYRIN), fluidized bed chlorination, melt chlorination, and otherchlorination processes. The total level of chlorine introduced to thepolymer can vary depending upon the product needs and the processcapabilities. Typical commercial grades range from 25-42 wt percentchlorine, although it is possible to go beyond this range. Chlorinationof the base resins may take place in suspension, solution, solid stateor fluidized bed. Free radical suspension chlorination processes aredescribed in U.S. Pat. Nos. 3,454,544, 4,767,823, each incorporatedherein by reference, and references cited therein. Such processesinvolve preparation of an aqueous suspension of a finely dividedethylene polymer, which is then chlorinated. An example of a freeradical solution chlorination process is disclosed in U.S. Pat. No.4,591,621, incorporated herein by reference. The polymers may also bechlorinated in the melt or fluidized beds, for example, as taught inU.S. Pat. No. 4,767,823, incorporated herein by reference.

A variety of ethylene-containing feedstocks with varying densities canbe used in the chlorination process. The limiting factor in most casesis the process by which the chlorination takes place (solution, slurry,etc.).

The placement of chlorine on the backbone can be varied, via thechlorination process, to produce resins that have a random distributionof chlorine, or a block distribution of chlorine. An example of a randomdistribution of chlorine includes roughly one chlorine per every fivecarbon atoms in a 36 weight percent chlorine containing polymer. Anexample of a block distribution of chlorine includes polymers sequencesalong the polyethylene backbone that are heavily chlorinated (onechlorine per every two carbon atoms), and adjacent sequences along thesame backbone that are primarily composed of ethylene. Polymerscontaining both random and block distributions of chlorine are alsoincluded with the scope of the invention. In a preferred embodiment, thepolymer contains a random distribution of chlorine along the backbone ofthe molecular chains of the polymer sample.

EXAMPLES

The following examples illustrate the present invention but are notintended to limit the scope of the invention. The examples of theinvention demonstrate that the addition of a soluble nitrogen containingchelating agent reduces the inconsistency of the cure rate, associatedwith contamination of the composition with zinc oxide, when crosslinkinghalogenated elastomers with polymercapto compound, basic metal oxide,and accelerator cure systems. They also demonstrate that the improvementin consistency of the cure rate is accomplished without inducingnegative changes in the vulcanization reaction or the resultant physicalproperties of the vulcanizate.

The compositions of the examples are listed in Tables 1 and 4, whichalso list the source for all materials. All ingredient amounts are basedon 100 parts by weight of the halogenated elastomer. ComparativeExamples A and B show the effect of ZnO contamination without theaddition of the nitrogen containing chelating agent. Examples 1 and 2show the effect of ZnO contamination in the presence of1,10-phenanthroline as the chelating agent. Examples 3 and 4 show theeffect of ZnO contamination in the presence of a polyamine as thechelating agent.

Each of the compositions in Tables 1 and 4 was mixed using a Banbury® BRinternal mixer (Farrel Corporation). The dry ingredients were charged tothe mixer first, followed by the liquid ingredients, and then thehalogenated elastomer. A slow mixing speed was used. The Banbury chutewas swept down after the compound had fluxed and was dumped from themixer at 105° C. The compound discharged from the mixer was placed on a6 inch×13 inch two roll mill and was rolled as it came off the mill.This mill procedure was repeated an additional 5-6 times to ensureadequate dispersion of all the ingredients. The final sheet was obtainedfrom the mill in a thickness of approximately 3 mm. Samples cut fromthis final sheet were used to measure cure rates and to compression moldplaque samples for testing the physical properties of the vulcanizate.

TABLE 1 Compositions of Comparative Examples A and B and Examples 1 and2 of the Invention Comparative Comparative Ex. 1, Ex. 2, IngredientSupplier Ex. A, phr Ex. B, phr phr phr Chlorinated Polyethylene Dow 100100 100 100 Tyrin ® CM 0836 Carbon Black, N-774 Sid 50 50 50 50Richardson Carbon Co. Magnesium Hydroxide, Harwick 5 5 5 5 StanMag ®Hydroxide B Aromatic Oil, Sundex ® 790T Sunoco, 30 30 30 30 Inc2-mercapto-1,3,4- Harwick 2.67 2.67 2.67 2.67 thiadiazole-5-thiobenzoate, Mastermix ® MB 4842, 75 percent Active TetrabutylammoniumHarwick 0.66 0.66 0.66 0.66 bromide, Mastermix ® MB 4988, 50 percentactive Zinc Oxide, ZnO-85, 85 Rhein 0.14 0.14 percent active Chemie1,10-phenanthroline Aldrich 1 1

Cure rate testing was accomplished according to ASTM D2084 on a MonsantoOscillating Disk Rheometer (ODR), at 177° C. Samples for physicalproperty testing were compression molded at 177° C. on a PHI RubberPress. Cure times were determined from the ODR cure rate test using thet₉₀ cure time plus an additional 10 percent. The t₉₀ time is the time,in minutes, for the sample to reach 90 percent of the final torqueobserved during the test. Physical property testing on the compressionmolded vulcanizates was conducted according to ASTM D412.

Table 2 lists the cure rate data obtained for Comparative Examples A andB and Examples 1 and 2 of the invention. The ODR test was run for 25minutes for all the examples. The data for Comparative Examples A and Bshows that the cure rate has been markedly depressed by the addition ofZnO. This is shown most clearly by the large increase in t₅₀, which isthe time for the torque to reach 50 percent of change between theminimum (ML min) and the maximum (MH max), and the corresponding t₉₀,which is the time for the sample to reach 90 percent of the torquedifference. The MH max in Comparative Example B is also much less thanin Comparative Example A, indicating that by the end of the test, thesample was not finished crosslinking. In contrast, Examples 1 and 2 ofthe present invention have markedly reduced differences in the cure rateparameters as shown in Table 2.

TABLE 2 Cure Parameters of Comparative Examples A and B and Examples 1and 2 of the Invention Comparative Comparative Example A Example BExample 1 Example 2 ML min (in-lb) 15.52 13.54 16.55 16.46 [cm-kg][17.88] [15.60] [19.06] [18.96] MH max (in- 54.02 36 58.34 56.7 lb)[62.23] [41] [67.20] [65.31] [cm-kg] ts1 (minutes) 1.03 2.57 0.99 0.92ts2 (minutes) 1.18 3.38 1.12 1.06 t2 (minutes) 0.98 2.06 0.95 0.88 t₅₀(minutes) 2.93 10.79 2.37 2.8 t₉₀ (minutes) 8.96 21.4 5.71 7.37 MAX-MIN38.5 22.46 41.79 40.24 (in-lb) [44.35] [25.87] [48.14] [46.35] [cm-kg]

The physical properties of the vulcanizates obtained by curing andcompression molding are shown in Table 3. Elongation at break andultimate tensiles of the Examples 1 and 2 are superior to ComparativeExamples A and B in every case. In addition there is no negative effecton vulcanizate properties by addition of the nitrogen containingchelating agent according to the present invention.

TABLE 3 Physical Properties of the Vulcanizates of Comparative ExamplesA and B and Examples 1 and 2 of the Invention Comparative ComparativeExample A Example B Example 1 Example 2 M50 (psi) 150 151 134 122[kg/cm²] [10.5] [10.6] [9.42] [8.58] M100 (psi) 632 592 549 516 [kg/cm²][44.4] [41.6] [38.6] [36.3] M200 (psi) 1249 982 924 879 [kg/cm²] [87.8][69.0] [65.0] [61.8] Ultimate 2548 2284 2698 2599 Tensile (UT) [179.1] [160.5]  [189.6]  [182.7]  (psi) [kg/cm²] Elongation 544 684 736 725 @UT (percent) Tensile @ 2548 2281 2698 2599 Break (psi) [179.1]  [160.3] [189.6]  [182.7]  [kg/cm²] Elongation @ 544 685 736 725 Break (percent)Hardness, 72 73 71 71 Shore A

Table 4 shows the compositions of Comparative Examples A and B andExamples 3 and 4 of the invention where a polyamine is used as anitrogen containing chelating agent. The cure rate parameters andphysical properties of the vulcanizates are listed in Tables 5 and 6,respectively. The polyamine used, in addition to providing protectionagainst ZnO contamination, also accelerates the cure rate parameters.Examples 3 and 4 show that in the presence of a significant amount ofZnO, the cure rate parameters do not change when the polyamine ispresent in the composition in accordance with the invention.

TABLE 4 Composition of Comparative Examples A and B and Examples 3 and 4of the Invention Comp. Ex. Comp. Ex. Ex. 3, Ex. 4, Ingredient SupplierA, phr B, phr phr phr Chlorinated Polyethylene Dow 100 100 100 100Tyrin ® CM 0836 Carbon Black, N-774 Sid 50 50 50 50 Richardson CarbonCo. Magnesium Hydroxide, Harwick 5 5 5 5 StanMag ® Hydroxide B AromaticOil, Sundex ® Sunoco, Inc 30 30 30 30 790T 2-mercapto-1,3,4- Harwick2.67 2.67 2.67 2.67 thiadiazole-5- thiobenzoate, Mastermix ® MB 4842, 75percent Active Tetrabutylammonium Harwick 0.66 0.66 0.40 0.40 bromide,Mastermix ® MB 4988, 50 percent active Zinc Oxide, ZnO-85, 85 Rhein 0.140.14 percent active Chemie Polyethyleneimine, Aldrich 2 2 Mn ~ 600

TABLE 5 Cure Parameters for Comparative Examples A and B and Examples 3and 4 of the Invention Comparative Comparative Example A Example BExample 3 Example 4 ML min (in-lb) 15.52 13.54 22.2 20.4 [cm-kg] [17.88][15.60] [25.6]  [23.5] MH max (in-lb) 54.02 36 52.15 49.2 [cm-kg][62.23] [41]  [60.07] [56.7] ts1 (minutes) 1.03 2.57 0.83 0.78 ts2(minutes) 1.18 3.38 0.99 0.93 t2 (minutes) 0.98 2.06 0.76 0.7 t50(minutes) 2.93 10.79 2.83 2.77 t90 (minutes) 8.96 21.4 7.17 7.29 MAX-MIN38.5 22.46 29.95 28.8 (in-lb) [cm-kg] [44.3]  [25.87] [34.50] [33.2]

TABLE 6 Physical Properties of the Vulcanizates of Comparative ExamplesA and B and Examples 3 and 4 of the Invention Comparative ComparativeExample A Example B Example 3 Example 4 M100 (psi) 632 592 1004 730[kg/cm²] [44.4]   [41.6] [70.57] [51.3]  M200 (psi) 1249 982 1983 1694[kg/cm²] [87.80]  [69.0] [139.4] [119.1] Ultimate 2548 2284 2546 2748Tensile (UT) [179.1] [160.5] [179.0] [193.2] (psi) [kg/cm²] Elongation @544 685 287 357 Break (percent) Hardness, 72 73 70 71 Shore A

What is claimed is:
 1. An article obtained from curing of a compositionconsisting of: a) a polymercapto crosslinking agent, b) a vulcanizationaccelerator, c) an inorganic base, d) a nitrogen containing chelatingagent, wherein the nitrogen containing chelating agent is selected fromthe group consisting of 1,10-phenanthroline and 2,2-bipyridyl, andpolyethylenimine; and e) a halogenated elastomer; wherein said nitrogencontaining chelating agent is soluble in said halogenated elastomer. 2.The article of claim 1, wherein the polymercapto crosslinking agent is2,5-dimercapto-1,3,4-thiadiazole or a derivative thereof.
 3. The articleof claim 1, wherein the polymercapto crosslinking agent is2-mercapto-1,3,4-thiadiazole-5-thiobenzoate.
 4. The article of claim 1,wherein the vulcanization accelerator is selected from the groupconsisting of quaternary ammonium or phosphonium salts, tertiary amines,and dihydropyridine derivatives.